TW201629192A - Flame retardant, and flame-retardant resin composition containing same - Google Patents

Abstract

A flame retardant containing as a main component an organic phosphorus compound represented by general formula (I): (in the formula, R is a hydrogen atom or a C1-4 alkyl group or monochloroalkyl group, Y is a C3-6 alkylene group or a group represented by -CH2CH2(OCH2CH2)zOCH2CH2- (z is an integer of 0-3), n is an integer of 0-10), wherein the flame retardant has a contained amount of a compound represented by general formula (II): (in the formula, R, Y, and n are defined the same as in general formula (I)) of 4 area% or less when the flame retardant is measured by gel permeation chromatography (GPC); and a flame-retardant resin composition containing this flame retardant and a resin.

Description

Flame retardant and flame retardant resin composition containing the same Field of invention

The present invention relates to a flame retardant and a flame retardant resin composition containing the same. More specifically, the present invention relates to a flame retardant for a resin, particularly a flame retardant containing an organophosphorus compound as a main component and a flame retardant resin composition containing the same, which is used as a polyurethane foaming material. The additive flame retardant at the time of flame retarding exhibits excellent flame retardancy and imparts excellent foaming properties and physical properties to the polyurethane foam material.

Background of the invention

In order to impart flame retardancy to the resin, a method of adding a flame retardant at the time of preparing a resin molded article is employed. The flame retardant includes an inorganic compound, an organic phosphorus compound, an organic halogen compound, a halogen-containing organic phosphorus compound, etc., and in this case, an organic halogen compound and a halogen-containing organic phosphorus compound exhibit excellent flame retarding effects. On the practical side, a flame retardant which can obtain a good flame retardant effect is an organic phosphorus compound, and particularly widely used are organic phosphates and halogen-containing organic phosphates.

Among a wide variety of resins, polyurethane foams (foams) are limited in their use due to their flammability, and in recent years, they have been flame retarded. Various studies have been conducted but are still insufficient.

Conventionally, as a flame retardant for polyurethane, ginseng (2-chloroethyl) phosphate, gin (chloropropyl) phosphate, ginseng (dichloropropyl) phosphate, and ginseng (2,3-dibromopropyl) are used. Phosphate esters, etc.

When ginseng (2-chloroethyl) phosphate and ginseng (dichloropropyl) phosphate are blended into a soft polyurethane foam, the flame retardant effect will be exhibited in the initial stage, but the flame retardant effect will follow. The time is significantly reduced, the anti-fogging property is poor, and there are many problems such as volatile organic compounds (VOC). This is considered to be due to the fact that the molecular weight of these compounds is small and the flame retardant will volatilize.

Further, the ginseng (2,3-dibromopropyl) phosphate ester is excellent in flame retardancy and sustainability, but has poor heat resistance, and is added to a soft polyurethane foaming material to produce a foamed material. It is not appropriate to have a burnt situation. Further, although ginseng (2,3-dibromopropyl) phosphate is also used as a flame retardant for polyester fibers, it is not used because of its carcinogenicity.

After that, as a flame retardant for a soft polyurethane foaming material, there is 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate) (for example, refer to Patent Document 1: US Patent No. Compound No. 3,192,242) and bismuth (2-chloroethyl)-extended ethyl diphosphate (for example, refer to Patent Document 2: JP-A-49-43272), and other compounds having two phosphorus atoms in one molecule are attracting attention. .

However, these compounds have to use chlorine gas at the time of production, have problems in the production surface, and are insufficient in terms of flame retardancy or sustainability.

In order to improve this part, the bis(2-chloroethoxy)phosphinyl group was used. (Diethyl)ethyl]phosphate, 2-chloroethyl bis[bis(2-chloroethoxy)phosphinyl (diethyl)ethyl]phosphate, oxy-2,1-ethane The dibasic bismuth (2-chloroethyl) bisphosphate has been examined (see, for example, Japanese Laid-Open Patent Publication No. SHO-48-96649

However, these compounds produce by-products of phosphorus compound monomers such as bis(2-chloroethyl) phosphate or ginyl (chloropropyl) phosphate at the time of production, and have problems such as poor antifogging property and high VOC.

Then, a halogen-containing condensed phosphate having a low content of a phosphorus compound and a low fogging property and a small amount of VOC has been examined (see, for example, Japanese Laid-Open Patent Publication No. Hei 8-259577).

Advanced technical literature Patent literature

Patent Document 1: US Patent No. 3192242

Patent Document 2: Japanese Patent Publication No. Sho 49-43272

Patent Document 3: Japanese Patent Laid-Open No. 48-96649

Patent Document 4: Japanese Patent Laid-Open No. 56-36512

Patent Document 5: Japanese Patent Laid-Open No. Hei 8-259577

Summary of invention

However, the halogen-containing condensed phosphate of Patent Document 5 is known to contain an impurity of a phosphorus compound having one hydroxyl group in the molecule, which is a by-product produced when the phosphate ester is produced.

When a halogen-containing condensed phosphate containing a phosphorus compound having such a hydroxyl group is added as a flame retardant to a resin, a transesterification reaction occurs with a terminal molecule of the resin, and there is a problem that the molecular weight of the resin is lowered. Further, when the resin is a polyurethane foam material, it may react with the isocyanate at the time of foaming to form a terminal of the polyurethane molecule, and the molecular weight of the polyurethane ester may be inhibited from increasing, and as a result, the physical properties of the polyurethane foam material may also be lowered.

Further, it also affects the bubble generation or state of the foam, and the adjustment when it is desired to manufacture the polyurethane foam having the same air permeability becomes unfavorable. Especially in the case of industrial production, the quality of the polyurethane foam material will become uneven and unsuitable.

As described above, in the technique described in Patent Document 5, which aims to reduce the VOC, attention has been paid to the reduction of impurities (by-products) of the halogen-containing condensed phosphate ester, particularly the reduction of the phosphorus compound, and the phosphorus compound having a hydroxyl group. Existence and its by-products are completely ignored.

Therefore, an object of the present invention is to provide a flame retardant for a resin, particularly a flame retardant containing an organophosphorus compound as a main component and a flame retardant resin composition containing the same, which is used as a flame retardant resin for blocking a polyurethane foam The additive flame retardant at the time of combustion can exhibit excellent flame retardancy and can impart excellent foaming properties and physical properties to the polyurethane foam material.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a polyphosphoric acid organophosphorus compound having a content of an organic phosphorus compound having a single hydroxyl group and a phosphate monomer content in a molecule satisfies a flame retardant for a resin, and particularly satisfies Most of the conditions for flame retardants for polyurethane foams are an excellent The flame retardant is capable of completing the present invention.

Therefore, according to the present invention, there can be provided a flame retardant containing the organophosphorus compound represented by the general formula (I) as a main component:

Wherein R is a hydrogen atom or an alkyl or monochloroalkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms or is -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _z OCH ₂ CH ₂ - (z is an integer represented by an integer of 0 to 3), n is an integer of 0 to 10]; and when the flame retardant is determined by gel permeation chromatography (GPC), the general formula (II) The content of the compound shown is 4 area% or less:

[wherein, R, Y and n are synonymous with the general formula (I)].

Further, according to the present invention, a flame retardant resin composition containing the above flame retardant and a resin can be provided.

According to the present invention, a flame retardant of a resin, in particular, a flame retardant containing an organophosphorus compound as a main component and a flame retardant tree containing the same can be provided. In the fat composition, the organic phosphorus compound exhibits excellent flame retardancy as an additive flame retardant when the polyurethane foaming material is flame-retarded, and can impart excellent foaming properties and physical properties to the polyurethane foam material.

The flame retardant of the present invention can further exert the above-described excellent effects in the case where the organophosphorus compound is dioxo-2,1-ethanediylphosphonium (2-chloro-1-methylethyl) phosphate.

Further, the flame-retardant resin composition of the present invention can further exert the above-described excellent effects in the case where any of the following requirements are satisfied, and the essential components are: the resin is selected from the group consisting of polyurethane resin, acrylic resin, phenol resin, epoxy resin, a resin of a vinyl chloride resin, a polyamide resin, a polyester resin, an unsaturated polyester resin, a styrene resin, and a synthetic rubber; a polyurethane resin is a polyurethane foam; and a flame retardant resin composition is 100 parts by mass relative to the resin A flame retardant is contained in a ratio of 1 to 40 parts by mass.

Form for implementing the invention

Flame retardant

The flame retardant of the present invention is characterized by containing an organophosphorus compound represented by the formula (I) (hereinafter also referred to as "compound (I)") as a main component: [Chemical 3]

Wherein R is a hydrogen atom or an alkyl or monochloroalkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms or is -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _z OCH ₂ CH ₂ - (z is an integer represented by an integer of 0 to 3), n is an integer of 0 to 10]; and when the flame retardant is determined by gel permeation chromatography (GPC), the general formula (II) The content of the compound shown (hereinafter also referred to as "compound (II)") is 4 area% or less:

[wherein, R, Y and n are synonymous with the general formula (I)].

The flame retardant of the present invention contains the compound (I) as a main component and contains a trace amount of impurities which are produced by the side during the production process, and is strictly a flame retardant composition.

The term "principal component" as used in the present invention means a content having 50% by area or more of the flame retardant of the present invention. The content (area%) of the compound (I) may be selected from 55, 60, 65, 70, 75, and 80, but is preferably 80% by area or more as described later.

Here, the content of the compound (II) measured by the GPC method is "4 area% or less" means that the content is "more than 0 area% and is 4 area% or less".

The specific content (area%) of the compound (II) under the GPC measurement is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 and 4.0, etc.

Further, the lower limit thereof is preferably 0.01 area%, more preferably 0.001 area%, more preferably 0.0001 area%, and the upper limit thereof is preferably 3.8 area%, more preferably 3.5 area%, more preferably 3.4 area%.

The compound (II) is a compound (by-product, also referred to as "half ester") which is produced by hydrolysis in the production of the compound (I), and has one hydroxyl group in the molecule. Therefore, when it is added as a flame retardant to a resin, a transesterification reaction occurs with the terminal molecule of the resin, and the molecular weight of the resin is lowered. In particular, when the resin is a polyurethane foam material, it reacts with the isocyanate to form a terminal of the polyurethane molecule at the time of foaming, and inhibits foaming or molecular weight increase of the polyurethane, and as a result, the physical properties of the polyurethane foam material are also lowered.

Therefore, although the flame retardant of the present invention is preferably free of the compound (II), since the production of the compound (I) cannot completely prevent the generation of by-products, the content of the compound (II) under the GPC measurement must be It should be below 4 area%.

In addition, the measurement of gel permeation chromatography (GPC: Gel Permeation Chromatography) will be described in detail in the examples.

Further, the content of the compound (I) in the GPC measurement is preferably 80 area% or more, more preferably 85 area% or more, and still more preferably 90 area% or more.

The specific content (area%) of the compound (I) under the GPC measurement is 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, 99, and 99.5.

Further, the upper limit of the content is theoretically 100 area%, but is preferably 98 area%, more preferably 96 area%, more preferably 95 area%.

The content of the compound (I) means the total amount of the compound of the formula (I) having a coefficient of n = 0 to 10. In fact, as in the examples n = 0, the compound is 50 to 75% of the total amount and the compound of n = 1 is 20 to 25% of the total amount, and the rest is a compound of n≧2.

When the content of the compound (I) is less than 80% by area, when it is added as a flame retardant to the resin, sufficient flame retardancy may not be imparted to the resin.

When the flame retardant is measured by gel permeation chromatography (GPC), the content of the compound of the formula (III) (hereinafter also referred to as "compound (III)") is 7 area%. The following is better, preferably 6 area% or less:

[wherein, R is synonymous with the general formula (I)].

Here, the content of the compound (III) measured by the GPC method is "7 area% or less", which means that the content is "more than 0 area% and is 7 sides". The product is less than %."

The specific content (area%) of the compound (III) under the GPC measurement is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5 and 7.0, etc.

Further, the lower limit thereof is preferably 0.01 area%, more preferably 0.001 area%, more preferably 0.0001 area%, and a more suitable upper limit is 5 area%, more preferably 4 area%, and more preferably 3 area%.

The compound (III) is a monomeric phosphate (by-product) produced when the compound (I) is produced, and has a small molecular weight and is easily volatilized. Therefore, when it is added to a resin as a flame retardant, the content of a volatile organic compound (VOC) will become large, and fogging resistance will worsen.

Therefore, although the flame retardant of the present invention is preferably free of the compound (III), the content of the compound (III) under the GPC measurement is expected because the production of by-products cannot be completely prevented in the production step of the compound (I). It is 7 area% or less.

The substituent R of the formula (I) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a monochloroalkyl group.

The alkyl group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tertiary butyl group. Base. From the viewpoint of the high phosphorus content in the compound (I), a methyl group or an ethyl group is preferred, and a methyl group is preferred.

The monochloroalkyl group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include a chloromethyl group, a chloroethyl group, a chloropropyl group, and a chlorobutyl group. From In view of the fact that the phosphorus content in the compound (I) is high, a chloromethyl group or a chloroethyl group is preferred, and a chloromethyl group is preferred.

The substituent R is preferably a hydrogen atom, a methyl group, an ethyl group, a chloromethyl group or a chloroethyl group, and a hydrogen atom, a methyl group or a chloromethyl group is preferred, and a hydrogen atom or a methyl group is particularly preferred.

The substituent Y in the formula (I) is an alkylene group having 3 to 6 carbon atoms or represented by -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _z OCH ₂ CH ₂ - (z is an integer of 0 to 3) base.

The alkylene group having 3 to 6 carbon atoms may be either linear or branched, and examples thereof include a trimethylene group, a propyl group, a butyl group, a pentyl group, and a hexamethylene group. From the viewpoint that the phosphorus content in the compound (I) is high, among these, a trimethylene group and a propyl group are preferred.

The group represented by -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _z OCH ₂ CH ₂ - (z is an integer of 0 to 3) is a residue of an alkylene oxide, and specifically, according to the coefficient z, CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₃ OCH ₂ CH ₂ -. From the viewpoint that the phosphorus content in the compound (I) becomes high, among these, -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ - is used. Preferably, -CH ₂ CH ₂ OCH ₂ CH ₂ - is preferred.

The substituent Y is preferably a trimethylene group, a propyl group or a -CH ₂ CH ₂ OCH ₂ CH ₂ -.

The coefficient n of the formula (I) is an integer of 0 to 10.

If the coefficient n exceeds 10, the flame retardancy does not change, and only an excessive increase in viscosity leads to difficulty in use.

Since the coefficient n is changed, the viscosity of the compound (I) tends to increase. Therefore, the coefficient n may be appropriately determined depending on the type of the resin to be added, the physical properties of the resin to be obtained, the ease of production of the compound (I), and the like. However, it is generally preferably 0 to 5, and preferably 0 to 3.

The compound (I) as a main component of the flame retardant of the present invention may, for example, be oxydi-2,1-ethanediyl fluorenyl (2-chloroethyl) phosphate or oxy-2,1-phosphate Ethane diyl hydrazine (2-chloro-1-methylethyl) ester, oxy-2,1-ethanediyl bis[10-chloro-7-(2-chloroethoxy)-7-oxygen -3,6,8-tris-7-phosphon-1-yl]bis(2-chloroethyl) ester, poly[oxy[(2-chloro-1-methylethoxy)oxyphosphinyl) Oxy-1,2-ethanediyloxy-1,2-ethanediyl], α-(2-chloro-1-methylethyl)-ω-[[bis(2-chloro-1-) Methyl ethoxy) phosphinyl] oxo], di-2-(2-chloroethyl) oxyphosphate, and di-2,1-ethanediyl phosphide 2-Chloro-1-methylethyl) ester is preferred, and in this case, it is produced in the production example, and the dioxygen phosphate-2,1-ethanediyl group used in the evaluation of the examples. It is especially preferred that bis(2-chloro-1-methylethyl) ester.

2. Manufacture of flame retardants

The flame retardant of the present invention can be obtained by a production method such as the following two-stage reaction.

(1) First reaction step

The phosphorus oxychloride is reacted with an alkanediol or an oxyalkylene glycol to obtain a corresponding condensed dichlorophosphate of the following formula;

[wherein, Y and n are synonymous with the general formula (I)].

When the phosphorus oxychloride is continuously reacted with the alkanediol or the oxyalkylene glycol, an exothermic reaction is carried out to generate hydrogen chloride. At the same time, the phosphorus oxychloride of the raw material remains in the unreacted state and remains in the reaction system. The residual phosphorus oxychloride reacts with an alkylene oxide or a chloroalkylene oxide in the second reaction in the next step to produce a low molecular weight phosphate monomer, and the fogging property and flame retardancy are lowered.

Then, the generated hydrogen chloride and the unreacted phosphorus oxychloride remaining in the system were removed under reduced pressure. That is, in the first reaction, phosphorus oxychloride is continuously supplied to the reaction tank for reaction with an alkanediol or an oxyalkylene glycol, wherein the ratio of phosphorus oxychloride to alkylene glycol or oxyalkylene glycol is from 1.5 to 3.0. The molar ratio of 1.0 is preferably an amount of phosphorus oxychloride relative to the alkanediol or oxyalkylene glycol, specifically a molar ratio of 1.7 to 2.0:1.0.

The reaction temperature is from 0 to 50 ° C, preferably from 15 to 20 ° C, and the generated heat can be removed by passing the refrigerant into a jacket or a coil attached to the reaction vessel. The resulting condensed dichlorophosphate is unstable due to heat, and it is necessary to remove hydrogen chloride and residual phosphorus oxychloride as much as possible at a low temperature and for a short time. Here, hydrogen chloride and phosphorus oxychloride are removed under the conditions of a temperature of 15 to 20 ° C, a degree of vacuum of 1 to 7 kPa, and a temperature of 20 ° C or less and a degree of vacuum of 0.1 to 1 kPa.

Further, by using a forced thin film distillation apparatus, the residual amount of hydrogen chloride and phosphorus oxychloride in the first reaction liquid can be minimized at a temperature of 16 to 20 ° C and a vacuum of 0.1 to 1 kPa.

Examples of the alkanediol used in the reaction include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 3-butanediol, 1,6-hexanediol, 2,4-hexanediol, 2,5-hexanediol, etc., but not limited to herein.

Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, and tetraethylene glycol, but are not limited thereto.

(2) Second reaction step

The condensed dichlorophosphate obtained in the first reaction is reacted with an alkylene oxide or a chloroalkylene oxide to obtain a halogen-containing condensed phosphate ester of the following formula, that is, a compound (I) for the purpose;

[wherein, R, Y and n are synonymous with the general formula (I)].

If the condensed dichlorophosphate is reacted with an alkylene oxide or a chloroalkylene oxide, the reaction will also be as exothermic as the first reaction. Since the condensed dichlorophosphate is unstable to heat, it becomes unstable, so the second reaction is more suitable as a continuous reaction than the batch reaction in which the heating time is long. If the heating time becomes longer, the condensed dichlorophosphate will thermally decompose and cause an undesirable side reaction. On the other hand, the continuous reaction causes the heating time of the condensed dichlorophosphate to be shortened, and the incidence of thermal decomposition and undesired side reactions is much less than that of the batch. In other words, it is preferred to supply the reaction product of the first reaction containing the condensed dichlorophosphate in a predetermined amount, and simultaneously supply the alkylene oxide or the chloroalkylene oxide corresponding to the reaction product to gradually react. Specifically, to use It is preferred that the tubular metering pump and the flow meter supply a reaction product of the first reaction with an alkylene oxide or a chloroalkylene oxide and allow both to react.

The alkylene oxide used in the reaction may, for example, be ethylene oxide, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide, but is not limited thereto. Among them, ethylene oxide and propylene oxide are preferred, and propylene oxide is preferred.

Examples of the chloroalkylene oxide include epichlorohydrin, etc., but are not limited thereto.

In the second reaction, a catalyst is used as an effective means, and for example, titanium tetrachloride can be used. The amount added is about 5 to 15 mils, preferably 9 to 13 mils, per mole of the condensed dichlorophosphate.

The theoretical amount of use of alkylene oxide or chloroalkylene oxide is calculated according to the following formula.

Theoretical usage (g) = (A × B × C) / (100 × 35.5)

[In the formula, A is the mass (g) of the condensed dichlorophosphate, B is the chlorine content (% by mass) of the condensed dichlorophosphate, and C is the molecular weight of the alkylene oxide or the chloroalkylene oxide, and 35.5 is Atomic amount of chlorine]

The actual use amount of the alkylene oxide or the chloroalkylene oxide is an excess of 10% by mass of the theoretical use amount to the theoretical use amount, and is preferably 2 to 6 mass% excess.

The excess amount of 6% by mass of the alkylene oxide or the chloroalkylene oxide is advantageous in that the ripening (maintenance) time necessary for the completion of the reaction can be shortened, but it is disadvantageous in terms of economical use in order to increase the amount of use.

The reaction temperature is 40 to 90 ° C, preferably 50 to 70 ° C. At a temperature of 40 ° C or lower, the progress of the reaction becomes very slow and practical, and at a temperature exceeding 90 ° C, a phenomenon in which the reaction liquid is colored or an amount of side reactants increases, and a high-quality product cannot be obtained.

In order to allow the reaction time necessary for the end of the reaction, the raw material is economically used for industrial-scale reaction for 5 to 30 hours, preferably in the range of 10 to 20 hours, for example, excess use of propylene oxide relative to the condensed dichlorophosphate. In the case where a continuous reaction is carried out at a reaction temperature of 55 to 60 ° C at 5 mass%, the residence time for obtaining a product of good quality is 10 to 20 hours, preferably 12 to 15 hours.

(3) Washing and dehydrating steps

The reaction mixture is discharged from the reactor and is subjected to a purification step such as a washing and dehydrating step.

The washing step is carried out by a generally known method, and any of a batch method, a continuous method, and the like can be carried out. Specifically, after the reactant is washed with a mineral acid solution such as sulfuric acid or hydrochloric acid, it is washed with alkali, washed with water, and dehydrated under reduced pressure. Alternatively, the reaction mixture is not washed with mineral acid, subjected to alkali washing, and the insoluble titanium compound (catalyst component) is removed by filtration or centrifugation in the produced water, washed with water, and dehydrated under reduced pressure.

The temperature of the washing step is 95 ° C or lower, preferably 85 ° C or lower, more preferably 70 ° C or lower, and more preferably 55 to 65 ° C.

The dehydration step is preferably carried out under reduced pressure. The temperature of the dehydration step is 120 ° C or less, preferably 110 ° C or less, more preferably 95 to 105 ° C, and the pressure is 10 kPa or less, preferably 1 to 5 kPa.

(4) Refining step

Then, in order to completely remove the low boiling component, a step of adding a refined product may also be added. The refining step is preferably carried out by vacuum distillation under water vapor. The temperature is below 120 ° C, preferably below 110 ° C, preferably from 95 to 105 ° C, and the pressure is Below 10 kPa, it is preferably 1 to 5 kPa.

In the above-described washing, dehydrating step and refining step, when the produced compound (I) is placed under a predetermined temperature condition in the presence of water, the compound (II) which forms a by-product by hydrolysis may be present.

3. Flame retardant resin composition

The flame-retardant resin composition of the present invention is characterized by containing the flame retardant of the present invention and a resin.

The flame retardant of the present invention is high in purity and high in quality, and can be used as a flame retardant for various thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include polyethylene resin, chlorinated polyethylene resin, polypropylene resin, polybutadiene resin, styrene resin, vinyl chloride resin, polyphenylene ether resin, polyphenylene sulfide resin, and polycarbonate. Resin, ABS (acrylonitrile-butadiene-styrene) resin, impact-resistant styrene resin, rubber modified styrene resin, SAN (styrene-acrylonitrile) resin, ACS resin, polyamide resin, polyfluorene Saturated or unsaturated polyester resin such as imine resin, PET (polyethylene terephthalate) resin and PBT (polybutylene terephthalate) resin, acrylic resin, polymethacrylic resin, polyether Ether ketone resin, polyether oxime resin, polyfluorene resin, polyarylate resin, polyether ketone resin, polyether nitrile resin, polythioether oxime resin, polybenzimidazole resin, polycarbodiimide resin, The liquid crystal polymer or the composite plastic may be used singly or in combination of two or more.

Further, examples of the thermosetting resin include an epoxy resin, a polyurethane resin, a polyimide resin, a phenol resin, a novolak resin, a resol resin, a polyether phthalimide resin, a melamine resin, a urea resin, and The saturated polyester resin or the diaryl phthalate resin may be used singly or in combination of two or more.

The resin which can make the flame retardant composition of the present invention fully exert its function, and is further selected from the group consisting of polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, and poly A resin of an ester resin, an unsaturated polyester resin, a styrene resin or a synthetic rubber is preferred, a polyurethane resin is preferred, and a polyurethane foam is preferred.

Here, the term "synthetic rubber" refers to a resin (elastomer) having rubber elasticity obtained by addition polymerization or copolymerization in the above-mentioned thermoplastic resin, and examples thereof include polybutadiene type, nitrile type, and chloroprene type. Ethylene and the like.

The amount of the flame retardant to be added may be appropriately set depending on the type of the resin to be added, the degree of flame retardancy desired, and the like. The flame retardant composition of the present invention is generally contained in an amount of 1 to 100 parts by mass based on the above-mentioned resin. 40 parts by mass of the flame retardant is preferred. When the amount of the flame retardant added is less than 1 part by mass, it is not preferable because sufficient flame retardancy of the resin cannot be imparted. On the other hand, when the amount of the flame retardant added exceeds 40 parts by mass, the physical properties of the resin component are lowered, and in particular, mechanical properties are lowered, which is not preferable.

The specific addition amount (parts by mass) of the flame retardant relative to 100 parts by mass of the resin is 1, 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40, and the like.

The flame retardant is preferably added in an amount of from 1 to 35 parts by mass, particularly preferably from 1 to 30 parts by mass.

The flame retardant resin composition of the present invention can be used as necessary. A known resin additive may be added to the extent that it does not adversely affect the physical properties of the resin, and other additives other than the flame retardant or the flame retardant may be contained. The amount of such a substance to be added can be appropriately set depending on the type of the resin, the degree of physical properties desired, and the like.

Examples of other flame retardants include non-triphenyl phosphate, cresyl phosphate, cresyl diphenyl phosphate, resorcinol-tetraphenyl bisphosphate, and bisphenol A-tetraphenyl bisphosphate. Halogen phosphate flame retardant; 2,2-bis(chloromethyl)-1,3-propanebis(chloroethyl)diphosphate, bismuth(2-chloroethyl)ethylene diphosphate, (poly) Halogen-containing phosphate ester-based flame retardant such as halogenated polyphosphate or bis(tribromo)neopentyl phosphate; decabromodiphenyl ether, tetrabromobisphenol A, 1,2-double (five) A bromine-based flame retardant such as bromophenyl)ethane; an inorganic flame retardant such as antimony trioxide or magnesium hydroxide; a nitrogen-based flame retardant such as ammonium polyphosphate or melamine phosphate.

Other additives other than the flame retardant include antioxidants, fillers, lubricants, modifiers, perfumes, antibacterial agents, pigments, dyes, heat-resistant agents, weathering agents, antistatic agents, ultraviolet absorbers, stabilizers, Strengthening agent, dripping agent, anti-caking agent, wood powder, starch, etc.

As described above, the present invention provides a flame retardant containing an organophosphorus compound as a main component and a flame retardant resin composition containing the same, which is used as an additive type when the polyurethane foaming material is flame-retarded. The flammable agent exhibits excellent flame retardancy and exhibits excellent foaming properties and physical properties of the polyurethane foam material.

The flame retardant of the present invention has a very low volatility of the compound (I) which is a main component, and can exert a flame retarding effect by being added to the resin, especially by a predetermined The prescription is added to the polyurethane foam material before foaming to exhibit an excellent flame retardant effect. As described later, the obtained polyurethane foam material exhibits excellent flame retardancy and foamability due to a flammability test such as MVSS-302.

That is, the flame-retardant polyurethane foaming material is superior in flame retardancy and durability, and excellent in fogging resistance, compared with the polyurethane foaming material which is flame-retarded by the current organophosphorus compound-based flame retardant. Performance.

A method for producing a polyurethane foam material is known, and a flame-retardant polyurethane foam material to which the flame retardant of the present invention is added can also be produced by a known method.

For example, 1 to 40 parts by mass of the flame retardant of the present invention is mixed with 100 parts by mass of a polyol containing a polyester polyol or a polyether polyol, and it is preferably 1 to 30 parts by mass. Further, the obtained mixture is stirred by adding a foam stabilizer, a catalyst, a foaming agent, etc., and then an organic polyisocyanate is added to carry out a reaction to obtain a flame-retardant polyurethane foam material.

The polyol is not particularly limited as long as it is generally used to form a polyurethane. However, it is suitable to use a polyester polyol having a molecular weight of about 2 to 8 hydroxyl groups per molecule and having a molecular weight of about 250 to 6500, and a polyether polyol. alcohol. When the molecular weight is less than 250, the activity is strong and it is not suitable for forming a polyurethane foam material. When the molecular weight is larger than 6,500, the viscosity is high and the workability is deteriorated.

Examples of the polyhydric alcohol include a glycol; a trihydric alcohol; and a polyhydric alcohol obtained by polymerizing ethylene oxide and/or propylene oxide using an amine such as sorbitol, sucrose or ethylene diamine as a starter. Wait.

Specific examples thereof include polyoxyethylene diol and polyoxypropylene diol. Polyols; polyoxyethylene glycerol, polyoxypropylene glycerol, poly(oxyethylene) poly(oxypropylene) glycerol, polyoxyethylene neohexane triol, polyoxypropylene penta hexane ternary Alcohol, poly(oxyethylene) poly(vinyl chloride) neohexane triol, poly(oxypropylene) 1,2,6-hexane triol, and polyoxypropylene alkanol, etc.; poly(oxygen) Ethylene) poly(oxypropylene) ethylene diamine; hexahydric alcohol such as polyoxyethylene sorbitol or polyoxypropylene sorbitol; octa alcohol such as polyoxyethylene sucrose or polyoxypropylene sucrose; and mixtures thereof.

Further, a special grade product such as a polyol dispersed in melamine or ammonium polyphosphate and a phosphorus-containing polyol may be mentioned.

Suitable polyhydric alcohols are polyether polyols which are poly(oxyethylene/oxypropylene) triols and have an average molecular weight in the range of from about 250 to 6500.

Examples of the organic polyisocyanate include tolylene diisocyanate, benzodiisocyanate, xylene diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, cyclopentane diisocyanate, and cyclohexane. Diisocyanate, isophorone diisocyanate, norbornane diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, and the like.

The foam stabilizer may, for example, be a silicone resin-based foam stabilizer (an oil) such as a decane-oxyalkylene block copolymer. Specifically, NIAX SILICONE L-580, L-590, L-620, L-638, L-638J, L-680, L-682, L-690, etc. by Momentive Performance Materials Co., Ltd. are mentioned.

The catalyst may be exemplified by triethylenediamine, dimethylethanolamine, and bis(2-dimethyl group). Aminoethyl)ether, N,N,N',N'-tetramethylhexylmethylenediamine, N,N',N'-trimethylaminoethylpiperazine, N-ethyl? Amine catalysts such as forint; tin-based catalysts such as stannous octoate and dibutyltin dilaurate.

As the blowing agent, a low boiling point compound such as water, fluorocarbon or methylene chloride (i.e., dichloromethane) can be used. As the dispersant, a nonionic surfactant such as an ether type, an ether ester type or an ester type can be used. Specific examples thereof include an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, decyl group, decyl group, dodecyl group, and thirteen group) and an aryl group (phenyl group). , tolyl, methylbenzyl, biphenyl, naphthyl) polyoxyethylene ether, alkyl aryl formaldehyde condensed polyoxyethylene ether, glycerol polyoxyethylene ether, polyethylene glycol fatty acid ester, propylene glycol ester, A glycerin polymer, a sorbitan ester, a fatty acid monoglyceride, a mixture of these, and the like.

Example

The present invention will be more specifically described by way of the examples and the comparative examples and the examples and comparative examples, but the scope of the invention is not limited by the examples.

The compounds (I), (II) and (III) in the products obtained in the production examples and the comparative production examples were analyzed by the following [GPC measurement], and the [acid value] of the product was measured by the following method. And [viscosity].

In addition, [flame retardancy], [compressive residual deformation], and [ventilation] of the foams obtained in the examples and the comparative examples were measured by the following methods, and the results of [compression residual deformation] were evaluated. Foaming].

[GPC measurement]

The product obtained in the production example and the comparative production example was used as a sample, and 10 ml of tetrahydrofuran (THF) was added to 0.05 g of each sample by using a pipette. The solution was analyzed by the following machine and analysis conditions, and the area % of the RI detector was defined as the content (composition) of each component of the compounds (I), (II) and (III).

In addition, the same product can be used with respect to the machine used.

(machine)

GPC analyzer (manufactured by TOSOH Co., Ltd., model: HLC-8220GPC)

Data analysis device (manufactured by TOSOH Co., Ltd., model: GPC-8020model II)

Protection column (manufactured by TOSOH Co., Ltd., model: TSK gel guardcolumn SuperHZ-L 4.6mml.D.×3.5cm)

Analysis column (manufactured by TOSOH Co., Ltd., model: TSK gel SuperHZ1000 4.6mml.D.×15cm)

Reference column (manufactured by TOSOH Co., Ltd., model: TSK gel SuperH-RC 6.0mml.D.×15cm)

(analysis conditions)

INLET temperature: 40 ° C

Column temperature: 40 ° C

RI temperature: 40 ° C

Solvent: tetrahydrofuran

Solvent flow rate: 0.35ml/min

RI (Refractive Index: Refractive Index)

Sample solution injection amount: 10 μl (annular tube)

(data processing conditions)

START TIME: 8.00

STOP TIME: 18.00 points

Detection sensitivity: 3mV / min

Base judgment value: 1mV/min

Exclusion area: 10mV × second

Exclusion height: 0mV

Exclude half value width: 0 seconds

[acid price]

The acid value (KOH mg/g) of the obtained product was measured in accordance with JIS K0070 Neutralization Titration.

[Viscosity] According to JIS Z8803, the viscosity (mPa‧s) of the obtained product was measured using a Ubum viscometer at a temperature of 25 °C.

[flame retardant]

The sample was cut out from the obtained foam, and a burning test was performed under the following conditions, and the burning distance (mm) was measured.

Test method: FMVSS-302 method (test method for safety standard of vehicle interior materials)

Horizontal burning test of polyurethane

Sample: thickness 10mm

[Compressed residual deformation]

The compression residual deformation (%) of the obtained foam was measured in accordance with JIS K6400-4 A.

[foaming property]

The foaming property of the obtained foam was evaluated based on the results of the compression residual deformation on the following basis.

○ (good foaming property): compression residual deformation is 10% or less

× (poor foaming): compression residual deformation exceeds 10%

[ventilation]

The air permeability (ml/cm ² /sec) of the obtained foam was measured in accordance with JIS L1096.

[Manufacturing Example 1]

(first reaction step)

A 1 liter capacity four-necked flask equipped with a condenser connected to a stirrer, a thermometer, a dropping funnel and a water scrubber was filled with 282.4 g (1.8 mol) of phosphorus oxychloride at a temperature of 16 to 18 ° C. It took 1 hour to drip diethylene glycol 106 g (1.0 mol) from a dropping funnel. After the completion of the dropping, the ripening reaction was carried out at the same temperature for 1 hour. Subsequently, the acid was removed under reduced pressure at the same temperature and a pressure of 1.3 kPa for 6 hours to remove hydrogen chloride and unreacted phosphorus oxychloride, and 307.1 g of a reaction product containing the condensed dichlorophosphate was obtained. Its chlorine concentration was 37.1% by mass.

(second reaction step)

To the reaction product obtained in the first reaction, 2.1 g (11 mmol) of titanium tetrachloride as a catalyst was added. The obtained reaction product and 195.4 g (3.4 mol) of propylene oxide were added to the reaction liquid at a temperature of 50 to 55 ° C for 3 hours to carry out a continuous reaction. After the addition, the reaction solution was heated to 80 ° C to carry out a ripening reaction for 2 hours. Its acid value is 0.8 KOHmg/g.

(washing, dehydration step)

The reaction product obtained in the second reaction is subjected to a purification step in batches. First, as a washing step, a concentration of 0.1% by mass of sulfuric acid water at a temperature of 60 ° C 100 g was added to the reaction liquid, and after stirring for 30 minutes, 3 g of sodium carbonate and 150 g of water were added to the reaction liquid, and the mixture was stirred for 30 minutes to carry out neutralization, and the aqueous phase was separated and allowed to stand. The oil phase was then washed with 250 g of water at the same temperature.

Next, the obtained reaction product was subjected to a reduced pressure dehydration step under a pressure of 100 ° C and 4 kPa.

(refining (water vapor vacuum distillation) step)

The obtained reaction product was subjected to a steam distillation under reduced pressure for 1 hour under the same conditions as the reduced pressure dehydration step.

The obtained compound has an acid value of 0.05 KOHmg/g and a viscosity of 900 mPa s (25 ° C). As a result of GPC analysis, the structural formula of the main component is a compound of the formula (I) wherein the substituent R is a methyl group and is a compound of the following formula. (I). Further, the content of the half ester component of the compound (II) was 0.9 area%, and the content of the monomer component of the compound (III) was 5.5 area%.

The results of GPC analysis, acid value and viscosity measurement are shown in Table 1.

[Manufacturing Example 2]

The compound of Production Example 2 was obtained in the same manner as in Production Example 1, except that the washing step was carried out at 85 °C.

[Manufacturing Example 3]

The compound of Production Example 3 was obtained in the same manner as in Production Example 1, except that the washing step was carried out at 95 °C.

[Comparative Manufacturing Example 1]

The compound of Comparative Production Example 1 was obtained in the same manner as in Production Example 1, except that the steam was distilled under reduced pressure at 160 ° C for 4 hours.

[Comparative Manufacturing Example 2]

The compound of Comparative Production Example 2 was obtained in the same manner as in Production Example 1, except that the water vapor vacuum distillation was carried out at 160 ° C for 8 hours.

The compositions and physical properties of Production Examples 1 to 3 and Comparative Production Examples 1 to 2 are shown in Table 1.

[Examples 1 to 3, Comparative Examples 1, 2, and Comparative Example 3 (control)]

(Manufacture of foam)

A soft polyurethane foam (foam) was produced by the following formulation, and the flame retardancy, foaming property, compression residual deformation, and air permeability were evaluated.

(Prescription: In this manual, “parts” means “parts by mass”)

‧Polyol [hydroxyl price: 56KOHmg/g]

100 copies

(Mitsui Chemical Co., Ltd., product name: ACTCOL T-3000)

‧Foaming agent [矽油]

1.0 part

(Momentive Performance Materials, product name: NIAX SILICONE L-638J)

‧catalyst [amine system: triethylene diamine]

0.2 parts

(Manufactured by Air Products and Chemicals, product name: Dabco 33-LV)

‧catalyst [amine system: bis(2-dimethylaminoethyl)ether]

0.04 parts

(made by Air Products and Chemicals, product name: Dabco BL-11)

‧catalyst [tin system: stannous octoate]

0.35 parts

(made by Air Products and Chemicals, product name: Dabco T-9)

‧ foaming agent (water)

4.3 copies

‧Blowing agent (methylene chloride)

8.0 copies

‧ flame retardant (shown in Table 2)

22 copies

‧ Isocyanate [toluene diisocyanate (TDI)]

The number of parts shown in Table 2

(Mitsui Chemical Co., Ltd., product name: COSMONATE T-80 (80/20), Index115)

The polyol, the foam stabilizer, the catalyst, the foaming agent and the flame retardant were prepared by the above prescription, and the mixture was uniformly mixed by stirring at a rotation speed of 3000 rpm for 1 minute using a stirrer. The isocyanate was then added and stirred at 3000 rpm for 5 to 7 seconds. Next, the preparation was immediately poured into a carton having a square (having a length of about 200 mm on one side) and a cube (having a height of about 200 mm).

The formulation will foam immediately and reach its maximum volume after a few minutes. Next, the obtained foam was allowed to stand in a furnace at a temperature of 120 ° C for 30 minutes to be hardened.

As a control test for the flame retardancy, a foam was produced and evaluated in the same manner as in Example 1 except that the flame retardant was not added (Comparative Example 3).

The obtained foam has a white soft communication bubble type cell structure.

The results obtained are shown in Table 2 together with a part of the formulation (mixing amount of flame retardant and isocyanate used).

[Table 2]

As is clear from the results of Table 2, the flame retardant of the present invention and the flame-retardant resin composition containing the same exhibit excellent flame retardancy under the desired conditions, and the foaming property of the polyurethane foam material and Physical properties are excellent.

On the other hand, the foams of Comparative Examples 1 and 2 have a large change in air permeability and compression residual deformation as compared with the foams of Examples 1 to 3. This result is considered to be because the compound (II) is a monofunctional compound, so that a polyfunctional alcohol having a large functionality and a large molecular weight reacts with an isocyanate more quickly, and the reaction of forming a common amine ester foaming material is interrupted, resulting in a normal amine ester. The formation of the foamed material is hindered and affects the physical properties of the amine ester foamed material. Therefore, the low compression residual deformability of the characteristics of the amine ester foam material is lost, and in addition, it is necessary to adjust the prescription when it is desired to manufacture a foam material having the same physical properties. Especially in the case of industrial production, the quality of the polyurethane foam material will become uneven and unsuitable.

Claims (6)

A flame retardant containing an organophosphorus compound represented by the general formula (I) as a main component: Wherein R is a hydrogen atom or an alkyl or monochloroalkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms or is -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _z OCH ₂ CH ₂ - (z is a group represented by an integer of 0 to 3), n is an integer of 0 to 10]; and when the flame retardant is determined by gel permeation chromatography (GPC), the formula (II) The content of the compound shown is 4 area% or less: [wherein, R, Y and n are synonymous with the general formula (I)]. The flame retardant of claim 1, wherein the organophosphorus compound is dioxo-2,1-ethanediylphosphonium (2-chloro-1-methylethyl) phosphate. A flame retardant resin composition containing the flame retardant of claim 1 or 2. The flame-retardant resin composition of claim 3, wherein the resin is selected from the group consisting of polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, A resin of styrene resin and synthetic rubber. The flame-retardant resin composition of claim 4, wherein the polyurethane resin is a polyurethane foam material. The flame-retardant resin composition according to any one of claims 3 to 5, wherein the flame-retardant resin composition contains the flame retardant in a proportion of 1 to 40 parts by mass based on 100 parts by mass of the resin.